Solid bath oil composition containing a clathrate

ABSTRACT

A solid bath oil composition containing bath oil adjuvant materials is prepared in the form of a dry,free-flowing powder or a molded configuration by utilizing urea, thiourea, or a mixture thereof as a clathrating agent to occlude the liquid, oily components of the bath preparation. The solid clathrate system thus formed releases theemollient oil upon contact with an aqueous medium.

United States Patent Fox et al.

1 Sept. 5, 1972 [54] SOLID BATH OIL COMPOSITION CONTAINING A CLATIIRATE[72] Inventors: Charles Fox; James Tassofl, both of Fairlawn, NJ.

[73] Assignee: Warner-Lambert Company,

ris Plains, NJ.

[22] Filed: April 3, 1968 [21] Appl. No.: 718,372

Related US. Application Data [63] Continuation-impart of Ser. No.487,623, Sept.

15, 1965, abandoned.

Mor-

2,559,583 7/1951 Barker ..424/322 X 2,665,256 1/1954 Barker ..424/322 XOTHER PUBLICATIONS Sagarin Cosmetics Science and Technology, 1957, pp.653 to 659.

Primary Examiner-Albert T. Meyers Assistant Examiner-Dale R. Ore

Attorney-Albert H. Graddis, Henry E. Millson, Jr. and Frank S. ChowABSTRACT A solid bath oil composition containing bath oil adjuvantmaterials is prepared in the form of a dry,freeflowing powder or amolded configuration by utilizing urea, thiourea, or a mixture thereofas a clathrating agent to occlude the liquid, oily components of thebath preparation. The solid clathrate system thus formed releasestheemollient oil upon contact with an aqueous medium.

14 Claims, No Drawings SOLID BATH OIL COMPOSITION CONTAINING ACLATI-IRATE CROSS REFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of our copending application, U.S. Ser. No.487,623, filed Sept. 15, 1965, now abandoned.

BACKGROUND OF THE INVENTION The advantages of particular bath oilpreparations and the wide use thereof is well known to the art.Typically, they are liquid oily preparations which are added to bathwater. Such preparations because of their liquid oily nature are awkwardand messy to use and to dispense. The oily preparations also severelylimit the types of components which may be included in any singlepreparation. For example, heretofore, it has been difficult orimpossible to add certain water softeners, marine algae, dry milksolids, sea salts and the like to prior bath oil preparations. Moreover,some bath oil preparations are subject to deterioration by oxidation.

The general concept of clathration compounds is well known to the art.For example, it is well known that certain organic Werner complexes arecapable of selectively occluding, either during or after formation ofcrystalline structures, certain other compounds within the crystallinestructure. Even compounds of similar chemical and physical propertiesmay be occluded to form clathration systems although to a much smallerextent than chemicals having dissimilar chemical and physicalproperties. The specific explanation for the phenomenon of clathrationis not known with certainty although present theories indicatethat themechanism may be explained on the basis of clathrate formation betweenthe occluding material and the material being occluded. The mechanism aswell as explanation of the theory of clathration have become confusedbecause of the use of different nomenclature for defining clathrationsystems. Clathration systems have been referred to by terms such asocclusion complexes, crystalline mixtures, adducts, and the like. Thesesystems, however, have in common the characteristic that the complexwhich is formed is not a true crystalline structure as the molecules ofone of the components are contained within the crystalline lattice ofthe occlusion component in non-stoichiometric proportions. Thecrystalline lattice framework may be in the form of channels, cages orlayers with the particular framework depending upon the moleculardimensions as well as other characteristics of the components involvedin forming the system. The complexes so formed are typically stable atordinary temperatures but melt or dissolve in similar fashion as theindividual components of the crystalline structure.

SUMMARY OF THE INVENTION This invention relates to a solid bath oilcomposition containing bath oil adjuvant materials, which is prepared inthe form of a dry,free-flowing and moldable powder by occluding theliquid, oily components of the bath preparation with urea and/orthiourea. The solid clathrate system formed releases the emollient oilor oils contained therein upon contact with an aqueous medium.

DESCRIPTION OF THE INVENTION It has now been found that thedisadvantages of prior oily bath preparations may be overcome byincorporating particular oils and especially emollient oils as clathratecompounds which take the form of finely divided, free-flowing powder.Urea is used as the clathrating agent for the emollient oils which havean essentially straight chain configuration in the molecule; a smallamount of branching, e.g. in isopropyl myristate, does not interferewith the clathration but for oils having predominantly branched chainsor cyclic structures, thiourea should be used in order to insure totalclathration. When a formulation of both straight chain and branchedchain oils is selected, both urea and thiourea should be used.

The advantages which accrue from our solid bath oil compositionsinclude, for example, the containment of easily oxidizable materials ofthe nature of highly unsaturated oils in a form protected from oxidationwhich otherwise occurs when such oils are retained in the liquid state.In addition, various powdered bath oil ad juvant materials may becombined with our solid ciathrate powders which could not previously beincluded in standard oily systems. For example, bath oil adjuvantmaterials including the following: water softeners, such as sodiumcarbonate, sodium carbonate monohydrate, sodium sesquicarbonate, andsodium tripoiyphosphate; marine algae, including the alginates(potassium alginate) and the carragheenates (Irish Moss); dry milksolids, such as powdered milk; sea salts, such as magnesium sulfate; andcoloring or tinting agents, may now be employed in combination with ourclathrate powders to form solid bath oil compositions which previouslywould have been difficult or impossible to formulate.

Various other additives may be combined with the oil or oils, prior toclathrate formation. For example, non-ionic surface active agents whichpromote spreading of the oils upon dissolution in an aqueous system maybe used. While all non-ionic surface active agents which arenon-irritating to the skin are operable in the solid bath oilpreparation of our invention, the ethers made by ethoxylating fattyalcohols such as lauryl, cetyl, myristyl, stearyl and oleyl alcohols areparticularly preferred. In particular, the condensates of between 2 to20 moles of ethylene oxide with cetyl alcohol are particularlypreferred.

Tinting or coloring agents may also be added to the emollient oils priorto clathrate formation to enhance the appearance of the final powderedbath oil composition.

Perfumes may be included in the solid bath oil preparations of ourinvention at any time, as desired. If added after the formation of theclathrate powder, the perfumes are absorbed on the surface of the solidbath oil particles. Inasmuch as the perfume does evaporate from such aproduct upon prolonged exposure to air, a more desirable perfumedproduct is obtained by combining the perfume oil with the emollient oilso it is contained within the clathrate system. As already discussed forthe emollient oil ingredients, a thiourea clathrating agent should beused if the perfume oil in use has a branched chain or cyclic structure.

The term bath oil adjuvant material" is meant to include any desirablebath additive which previously could not be added to a liquid oily bathcomposition. These materials are added in an amount sufficient toachieve the desired effect. Generally, minor amounts are added but thisamount will vary to a large extent, depending upon the nature of thematerial added and whether it is added alone or in combination withother bath oil adjuvant materials. Of course, the final product is adry, free-flowing and moldable powder.

In addition to preparing bath preparations as powders, other moldedforms are possible such as compressed tablets or various shapes andconfigurations which would have marketing advantages.

This invention, therefore, provides a new and novel clathration systemwherein oils are occluded within a clathrate system such that theresulting preparation is a dry, free-flowing and moldable powder.

The new and novel bath oil preparations of this invention in the form ofdry, free-flowing, or moldable powders, release the emollient oilstherein upon contact with an aqueous medium.

In preparing the new and novel bath preparation of the presentinvention, a clathrate system is formed by dissolving urea, thiourea, ora mixture thereof, and the desirable oil or combination of oils in asuitable solvent, such as a lower alcohol. Typically, methanol is used;however, other alcohols, such as ethanol, are also suitable. Theemollient oil or oils which can be occluded by the clathrating agent toform the product of this invention are of the class commonly used inbath oil preparations. Particularly preferred emollient oils are, forexample, isopropyl myristate, mineral oil, isopropyl stearate, isopropyllinoleate, oleyl alcohol, cetyl alcohol, tetrahydrogeranyl palmitate,isocetyl isostearate, and synthetic oils obtained by the reaction of amonohydroxy aliphatic alcohol with an alkylene oxide comprisingpredominantly l,2-propylene oxide. The synthetic polymer oils of thistype are described in U.S. Pat. No. 2,448,664 and are sold commerciallyas the UCON LB series of lubricants by Union Carbide Corp., N.Y., N.Y.They are water immiscible polymer products with lubricating propertieswhich have an average of at least 9 oxy-l ,2-propylene groups in eachmolecule. The alcohols which are reacted with the alkylene oxide to formthese polymer oils are normal or branched chain alcohols of one tocarbon atoms. The synthetic oil products of this type which arepreferred for use in this invention have a viscosity ranging from 65 to1,715 Saybolt seconds (1 1.75-37] centistokes) at 100 F The averagemolecular weight of the operable polymers is between 1,000 and 3,000calculated by acetyl values. Of these, one particular product, UCON LB1715, which has a viscosity of 1,715 Saybolt seconds at 100 F., isparticularly preferred. U.S. Pat. No. 2,668,150, patented Feb. 2, 1954,describes Ucon LB 1715 as the monobutyl ether of a polyoxypropylene diolhaving a molecular weight of approximately 2,000 to 2,100 derived by theaddition of 1,2-propylene oxide to butyl alcohol.

The components of the clathrate system in this invention are employed ina ratio of from about I to about 10 parts, preferably from about 1 toabout 5, and most preferably from about 3 parts by weight of urea perpart by weight of oil. If thiourea is employed, the

ratio should be from about 1 to about l0 parts, preferably from about 2to about 10 parts per part by weight of oil.

The solvent is employed in the clathrate system in an amount from about20 parts to about 40 parts by weight, based on the weight of the totalclathrate system.

The ingredients, in amounts prescribed, are combined and mixed whileheating to a temperature ranging from about 50 to about C. The heatedmixture is thereafter slowly cooled to room temperature (about 20 toabout 22 C.) and filtered. The solvent, for the most part, is removed inthe filtration step. The resulting crystals may thereafter be washed, ifdesired, with a suitable material such as ethyl ether or the like andthereafter the washed crystals may be air dried. The air dried crystalswhich may contain bath oil adjuvant materials within the clathrationsystem can be employed alone or in combination with other solid bath oiladjuvant materials such as water softeners, marine algae, dry milksolids, sea salts and the like. Such materials have not beensuccessfully added to prior art liquid bath oil preparations. Theprepared clathrate containing bath composition of our invention may beemployed as free-flowing powder or may be molded or compressed into anydesirable form such as tablets, various molded configurations or thelike.

The invention may be further exemplified by the following examples.

EXAMPLE 1 The following components in amounts indicated are combined andmixed while heating to a temperature of 5060 C. until the mixturebecomes clear:

isopropyl Myristate l part U rea 5 parts Methanol 20 parts The solutionis thereafter slowly cooled to room temperature in the open atmosphereand after reaching room temperature, the solution is filtered. Theresulting crystals so recovered are washed with ethyl ether and airdried to form a dry, free-flowing powder having an average particle sizeof about 20 to about 50 mils. An average particle size of 10 to aboutmils may also be prepared by methods known to the art. Upon addition ofthe dried particles to a water-containing environment, the occluded oilsare released and provide an oily film on the surface of the watercontaining environment.

The following preparations are prepared using the clathrate compound ofExample 1:

EXAMPLE 2 Clathrate compound 8 parts Dry Milk Solids 2 parts EXAMPLE 3Clathrate compound 8 parts Sodium tripolyphosphate l part Magnesiumsulfate l part EXAMPLE 4 isopropyl myristate 0.9 parts UCON LB 1715* 0.1parts Urea 5 parts Methanol 20 parts Trade marked product of UnionCarbide Company prepared as described in U.S.P. 2.448.664.

The clathrate obtained from this mixture is used as follows:

Sodium tripolyphosphate 5 parts Magnesium sulfate 5 parts Potassiumalginate 2 parts Perfume Oil 0.5 parts above clathrate 87.5 parts Whenadded to water this product quickly dissolves to leave a thin layer ofperfumed oil spread on the surface while softening the water to preventsoap curds.

The following compositions may also be formulated in accordance with theprocedure of the examples previously indicated:

EXAMPLE 5 Mineral Oil Lt. Tech. 9 parts Urea 5 parts Perfume Oil 0.]part Methanol 20 parts EXAMPLE 6 Mineral Oil Lt. Tech. 8 parts CetylAlcohol 0 1 part Urea pans Perfume Oil 0.l part Methanol 20 partsEXAMPLE 7 Mineral Oil Lt. Tech. 0.9 parts Elhoxylatcd Cetyl Alcohol 0.lpart (containing moles of ethylene oxide) Urea 5 parts Methanol partsEXAMPLE 8 Glycerol Monolaurate 0.8 parts Ethoxylated Cetyl Alcohol 0.]part (containing l0 moles of ethylene oxide) lsopropyl Stearate 0.! partUrea 5 parts Methanol 20 parts EXAMPLE 9 Mineral Oil Lt. Tech. I partlsocetyl Isostearate 0.9 pans Perfume Oil 0.! part Urea 5 parts Thiourea5 parts Methanol 20 parts EXAMPLE l0 isopropyl Linoleate 0.9 partsPerfume Oil 0.] part Urea 5 parts Methanol 20 parts EXAMPLE I lClathrate Compound 8 parts Potassium Alginate 2 pans EXAMPLE l2Clathrate Compound 8 parts lrish Moss 2 pans It is understood that theforegoing detailed descrip tion is given merely by way of illustrationand that many variations may be made therein without departing from thespirit of this invention.

What is claimed is:

1. A solid bath oil composition which comprises:

a. a clathrating agent selected from the group consisting of urea,thiourea and mixtures thereof;

b. at least one emollient oil selected from the group consisting ofisopropyl myristate, mineral oil, isopropyl stearate, isopropyllinoleate, oleyl alcohol, cetyl alcohol, tetrahydrogeranyl palmitate,isocetyl isostearate and a synthetic polymer oil ob tained by reactingbutyl alcohol with 1,2- propylene oxide, wherein said polymer has aviscosity of l7 l5 Saybolt seconds at l00F; and

c. at least one bath oil adjuvant material selected from the groupconsisting of sodium carbonate, sodium carbonate monohydrate, sodiumsesquicarbonate, sodium tripolyphosphate, potassium alginate, lrishMoss, dry milk solids, magnesium sulfate, and ethoxylated cetyl alcoholcontaining 10 moles of ethylene oxide; wherein the ratio of the oil tothe clathrating agent is from about 1 to about 10 parts by weight ofclathrating agent per part by weight of emollient oil.

2. A solid bath oil composition according to claim 1 wherein theclathrating agent is urea which is present in from about 1 to about 5parts by weight per part by weight of the emollient oil.

3. A solid bath oil composition according to claim 1 wherein theclathrating agent is thiourea which is present in from about 2 to about10 parts by weight per part by weight of emollient oil.

4. A solid bath oil composition according to claim I wherein theclathrate compound formed from (a) and (b) is present in an amount ofabout 8 parts by weight; and wherein the bath oil adjuvant material (c)is potassium alginate which is present in an amount of about 2 parts byweight.

5. A solid bath oil composition according to claim 1 wherein theclathrate compound formed from (a) and (b) is present in an amount ofabout 8 parts by weight; and wherein the bath oil adjuvant material (c)is Irish Moss which is present in an amount of about 2 parts by weight.

6. A solid bath oil composition comprising:

a. about 2 parts by weight of dry milk solids; and

b. about 8 parts by weight of a clathrate composition formed from about1 part by weight of isopropyl myristate and about 5 parts by weight ofurea.

7. A solid bath oil composition comprising:

a. about l part by weight of sodium tripolyphosphate;

b. about i partby weight of magnesium sulfate; and

c. about 8 parts by weight of a clathrate composition formed from about1 part by weight of isopropyl myristate and about 5 parts by weight ofurea.

8. A solid bath oil composition comprising:

a. about 5 parts by weight of sodium tripolyphosphate;

b. about 5 parts by weight of magnesium sulfate;

c. about 2 parts by weight of potassium alginate;

d. about 0.5 parts by weight of perfume oil; and

e. about 87.5 parts by weight of a clathrate composition, formed from:

I. about 0.9 parts by weight of isopropyl myristate;

2. about 01 part by weight of a synthetic polymer oil obtained byreacting butyl alcohol with 1,2- propylene oxide, said polymer oilhaving a viscosity of 1715 Saybolt seconds at 100F.; and

3. about 5 parts by weight of urea.

9. A solid bath oil composition comprising: a. about 0.9 parts by weightof Mineral Oil Light Technical;

b. about 5 parts by weight of urea; and

c. about 0.1 part by weight of perfume oil.

10. A solid bath oil composition comprising:

a. about 0.8 parts by weight Mineral Oil Light Technical;

b. about 0. 1 part by weight cetyl alcohol;

c. about 5 parts by weight urea; and

d. about 01 part by weight perfume oil.

11. A solid bath oil composition comprising:

a. about 0.9 parts by weight Mineral Oil Light Technical;

b. about 0.! part by weight ethoxylated cetyl alcohol containing 10ethylene oxide groups per mol; and c. about 5 parts by weight urea. 12.A solid bath oil composition comprising: a. about 0.8 parts by weightglycerol monolaurate; b. about 0.1 part by weight ethoxylated cetylalcohol containing 10 ethylene oxide groups per mol; c. about 0.1 partby weight isopropyl stearate; and d. about 5 parts by weight urea. 13. Asolid bath oil composition comprising: a. about 1 part by weight MineralOil Light Technical; b. about 0.9 parts by weight isocetyl isostearate;c. about 0.1 part by weight perfume oil; d. about 5 parts by weighturea; and e. about 5 parts by weight thiourea. 14. A solid bath oilcomposition comprising: a. about 0.9 parts by weight isopropyllinoleate; b. about 01 part by weight perfume oil; and c. about 5 partsby weight urea.

I i i

2. about 0.1 part by weight of a synthetic polymer oil obtained byreacting butyl alcohol with 1,2-propylene oxide, said polymer oil havinga viscosity of 1715 Saybolt seconds at 100*F.; and
 2. A solid bath oilcomposition according to claim 1 wherein the clathrating agent is ureawhich is present in from about 1 to about 5 parts by weight per part byweight of the emollient oil.
 3. A solid bath oil composition accordingto claim 1 wherein the clathrating agent is thiourea which is present infrom about 2 to about 10 parts by weight per part by weight of emollientoil.
 3. about 5 parts by weight of urea.
 4. A solid bath oil compositionaccording to claim 1 wherein the clathrate compound formed from (a) and(b) is present in an amount of about 8 parts by weight; and wherein thebath oil adjuvant material (c) is potassium alginate which is present inan amount of about 2 parts by weight.
 5. A solid bath oil compositionaccording to claim 1 wherein the clathrate compound formed from (a) and(b) is present in an amount of about 8 parts by weight; and wherein thebath oil adjuvant material (c) is Irish Moss which is present in anamount of about 2 parts by weight.
 6. A solid bath oil compositioncomprising: a. about 2 parts by weight of dry milk solids; and b. about8 parts by weight of a clathrate composition formed from about 1 part byweight of isopropyl myristate and about 5 parts by weight of urea.
 7. Asolid bath oil composition comprising: a. about 1 part by weight ofsodium tripoly-phosphate; b. about 1 part by weight of magnesiumsulfate; and c. about 8 parts by weight of a clathrate compositionformed from about 1 part by weight of isopropyl myristate and about 5parts by weight of urea.
 8. A solid bath oil composition comprising: a.about 5 parts by weight of sodium tripolyphosphate; b. about 5 parts byweight of magnesium sulfate; c. about 2 parts by weight of potassiumalginate; d. about 0.5 parts by weight of perfume oil; and e. about 87.5parts by weight of a clathrate composition, formed from:
 9. A solid bathoil composition comprising: a. about 0.9 parts by weight of Mineral OilLight Technical; b. about 5 parts by weight of urea; and c. about 0.1part by weight of perfume oil.
 10. A solid bath oil compositioncomprising: a. about 0.8 parts by weight Mineral Oil Light Technical; b.about 0.1 part by weight cetyl alcohol; c. about 5 parts by weight urea;and d. about 0.1 part by weight perfume oil.
 11. A solid bath oilcomposition comprising: a. about 0.9 parts by weight Mineral Oil LightTechnical; b. about 0.1 part by weight ethoxylated cetyl alcoholcontaining 10 ethylene oxide groups per mol; and c. about 5 parts byweight urea.
 12. A solid bath oil composition comprising: a. about 0.8parts by weight glycerol monolaurate; b. about 0.1 part by weightethoxylated cetyl alcohol containing 10 ethylene oxide groups per mol;c. about 0.1 part by weight isopropyl stearate; and d. about 5 parts byweight urea.
 13. A solid bath oil composition comprising: a. about 1part by weight Mineral Oil Light Technical; b. about 0.9 parts by weightisocetyl isostearate; c. about 0.1 part by weight perfume oil; d. about5 parts by weight urea; and e. about 5 parts by weight thiourea.
 14. Asolid bath oil composition comprising: a. about 0.9 parts by weightisopropyl linoleate; b. about 0.1 part by weight perfume oil; and c.about 5 parts by weight urea.